US8021606B2 - Hydrogen storage alloy, its production method, hydrogen storage alloy electrode, and secondary battery - Google Patents

Hydrogen storage alloy, its production method, hydrogen storage alloy electrode, and secondary battery Download PDF

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Publication number: US8021606B2
Authority: US; United States
Prior art keywords: hydrogen storage; storage alloy; denotes; phase; general formula
Prior art date: 2005-08-11
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.): Active, expires 2029-01-01

Application number

US12/063,391

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English (en)

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US20090104527A1 (en

Inventor

Tetsuya Ozaki

Tetsuo Sakai

Manabu Kanemoto

Minoru Kuzuhara

Tadashi Kakeya

Masaharu Watada

Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

National Institute of Advanced Industrial Science and Technology AIST

GS Yuasa International Ltd

Original Assignee

National Institute of Advanced Industrial Science and Technology AIST

GS Yuasa International Ltd

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2005-08-11

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2006-08-11

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2011-09-20

2006-08-11 Application filed by National Institute of Advanced Industrial Science and Technology AIST, GS Yuasa International Ltd filed Critical National Institute of Advanced Industrial Science and Technology AIST

2008-04-18 Assigned to GS YUASA CORPORATION, NATIONAL INSTITUTE OF ADVANCED INDSUTRIAL SCIENCE AND TECHNOLOGY reassignment GS YUASA CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KAKEYA, TADASHI, KANEMOTO, MANABU, KUZUHARA, MINORU, OZAKI, TETSUYA, SAKAI, TETSUO, WATADA, MASAHARU

2008-06-06 Assigned to GS YUASA CORPORATION, NATIONAL INSTITUTE OF ADVANCED INDUSTRIAL SCIENCE AND TECHNOLOGY reassignment GS YUASA CORPORATION CORRECTIVE ASSIGNMENT TO CORRECT THE ASSIGNEE PREVIOUSLY RECORDED ON REEL 020823 FRAME 0773. ASSIGNOR(S) HEREBY CONFIRMS THE CORRECT NAME OF ASSIGNEE TO NATIONAL INSTITUTE OF ADVANCED INDUSTRIAL SCIENCE AND TECHNOLOGY. Assignors: KAKEYA, TADASHI, KANEMOTO, MANABU, KUZUHARA, MINORU, OZAKI, TETSUYA, SAKAI, TETSUO, WATADA, MASAHARU

2009-04-23 Publication of US20090104527A1 publication Critical patent/US20090104527A1/en

2011-01-19 Assigned to GS YUASA INTERNATIONAL LTD reassignment GS YUASA INTERNATIONAL LTD ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GS YUASA CORPORATION

2011-09-20 Application granted granted Critical

2011-09-20 Publication of US8021606B2 publication Critical patent/US8021606B2/en

Status Active legal-status Critical Current

2029-01-01 Adjusted expiration legal-status Critical

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Images

Classifications

- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/24—Electrodes for alkaline accumulators
- H01M4/242—Hydrogen storage electrodes
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0031—Intermetallic compounds; Metal alloys; Treatment thereof
- C01B3/0047—Intermetallic compounds; Metal alloys; Treatment thereof containing a rare earth metal; Treatment thereof
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0031—Intermetallic compounds; Metal alloys; Treatment thereof
- C01B3/0047—Intermetallic compounds; Metal alloys; Treatment thereof containing a rare earth metal; Treatment thereof
- C01B3/0052—Intermetallic compounds; Metal alloys; Treatment thereof containing a rare earth metal; Treatment thereof also containing titanium
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0031—Intermetallic compounds; Metal alloys; Treatment thereof
- C01B3/0047—Intermetallic compounds; Metal alloys; Treatment thereof containing a rare earth metal; Treatment thereof
- C01B3/0057—Intermetallic compounds; Metal alloys; Treatment thereof containing a rare earth metal; Treatment thereof also containing nickel
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/383—Hydrogen absorbing alloys
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S420/00—Alloys or metallic compositions
- Y10S420/90—Hydrogen storage

Definitions

the present invention relates to a hydrogen storage alloy having a new phase as a crystal structure, its production method, a hydrogen storage alloy electrode, and a secondary battery using the hydrogen storage alloy electrode.
a hydrogen storage alloy is an alloy capable of safely and easily storing hydrogen as an energy source. Accordingly, the alloy has drawn lots of attention as a new energy conversion and storage material.
a nickel-hydrogen storage battery using a hydrogen storage alloy as a negative electrode material has following characteristics; (a) having a high capacity; (b) being hardly deteriorated even if supercharged or super discharged; (c) being capable of charging and discharging at high efficiency; and (d) causing no bad effect on the environment and is clean. Therefore, the battery has drawn attention as a consumer battery and its applications and practical uses have been actively promoted.
the hydrogen storage alloy has capabilities for various applications in terms of mechanical, physical, and chemical properties, it is listed as one of important materials in future industrial fields.
an electrode material for a nickel-hydrogen storage battery which is one application example of such a hydrogen storage alloy
AB 5 type rare earth-Ni type alloys having a CaCu 5 type crystal structure As an electrode material for a nickel-hydrogen storage battery, which is one application example of such a hydrogen storage alloy, are practically used AB 5 type rare earth-Ni type alloys having a CaCu 5 type crystal structure.
the discharge capacity of the alloy is limited to about 300 mAh/g and it is difficult to further increase the capacity in the present state.
Patent Document 1 discloses electrodes containing LaCaMgNi 9 alloys having a PuNi 3 type crystal structure.
Patent Document 2 discloses that electrodes containing rare earth-Mg—Ni type alloys having a CeNi 3 type, Gd 2 Co 7 type, or Ce 2 Ni 7 type structure show a good hydrogen releasing property while keeping high hydrogen storage capacities.
Patent Document 3 discloses that particles of hydrogen storage alloys having a Ce 5 Co 19 type crystal structure phase in the surface layer parts and whose composition is defined by a general formula AB x (x is 3.5 to 5) have a high reaction speed with hydrogen in a hydrogen absorption and desorption process.
Patent Document 1 Japanese Patent No. 3015885
Patent Document 2 Japanese Patent Application Laid-Open No. 11-323469
Patent Document 3 Japanese Patent No. 3490871
the AB 3 to 3.8 type rare earth type alloys disclosed in the above-mentioned three patent documents have a problem that although having high hydrogen storage capacities, the alloys are inferior in durability in the case of being used for secondary batteries as compared with the AB 5 type rare earth alloys.
the present invention aims to provide a hydrogen storage alloy and a hydrogen storage alloy electrode having a high hydrogen storage capacity and excellent in durability.
the invention also aims to provide a secondary battery having a high discharge capacity and scarcely decrease in the capacity retention ratio even after repeated charging and discharging. Further, the present invention also aims to provide a hydrogen storage alloy production method for efficiently producing a hydrogen storage alloy having a high hydrogen storage capacity and excellent in durability.
the present inventors have made various investigations to solve the above-mentioned problems and have found a hydrogen storage alloy having a new phase which is excellent in durability and has a high hydrogen storage capacity and have finally accomplished the invention.
a first aspect of the present invention provides a hydrogen storage alloy containing a phase of a chemical composition defined by a general formula A 5 ⁇ x B 1+x C 24 , wherein in the general formula A 5 ⁇ x B 1+x C 24 , A denotes one or more element(s) selected from rare earth elements; B denotes one or more element(s) selected from a group consisting of Mg, Ca, Sr, and Ba; C denotes one or more element(s) selected from a group consisting of Ni, Co, Mn, Al, Cr, Fe, Cu, Zn, Si, Sn, V, Nb, Ta, Ti, Zr, and Hf, and x denotes a numeral in a range from ⁇ 0.1 to 0.8 and the phase has a crystal structure belonging to a space group of R-3m and having a length ratio of the c-axis to the a-axis of the lattice constant in a range of 11.5 to 12.5.
the “rare earth elements” described in this description includes Y (yttrium).
phase in the first aspect defined by the general formula A 5 ⁇ x B 1+x C 24 , belonging to the space group of R-3m, and having a length ratio of the c-axis to the a-axis of the lattice constant in a range of 11.5 to 12.5, is described as an A 5 BC 24 phase for convenience.
the crystal structure belonging to the space group of R-3m belongs to a rhombohedral system.
the a-axis length and the c-axis length described in the first aspect is of a lattice constant in the case that the crystal structure is regarded as a hexagonal system but not a rhombohedral system. Accordingly, the a-axis length and the c-axis length in the first aspect are not equal.
a 5 ⁇ x B 1+x C 24 in the first aspect does not mean that the A 5 BC 24 phase contains no element other than A, B, and C. It naturally means that a trace amount of an element other than A, B, and C may be contained to an extent that the effect of the invention is not affected. For instance, as the element other than A, B, and C, a trace amount of molybdenum, tungsten, palladium, and platinum may be contained.
a third aspect of the present invention is characterized in that in the hydrogen storage alloy of the second aspect, the alloy contains La as R1 and both Ni and Co as R2.
a fourth aspect of the present invention is characterized in that in the hydrogen storage alloy of the first aspect, the crystal grain size of the hydrogen storage alloy is 10 to 100 nm.
a fifth aspect of the present invention is characterized in that in the hydrogen storage alloy of the first aspect, the phase contains at least one element of Mn and Al.
a sixth aspect of the present invention is characterized in that in the hydrogen storage alloy of the first aspect, A is one or more element(s) selected from La, Ce, Pr, and Y; B is Mg; and C is one or more element(s) selected from Ni, Co, Mn, Al, Fe, Cu, Zn, Si, Sn, V, Zr, and Hf.
a seventh aspect of the present invention is a hydrogen storage alloy electrode containing the hydrogen storage alloy of any one of the first to sixth aspects as a hydrogen storage medium.
An eighth aspect of the present invention is a secondary battery including the hydrogen storage alloy electrode of the seventh aspect as an anode.
a ninth aspect of the present invention is a method for producing a hydrogen storage alloy containing a phase of a chemical composition defined by a general formula A 5 ⁇ x B 1+x C 24 , wherein in the general formula A 5 ⁇ x B 1+x C 24 , A denotes one or more element(s) selected from rare earth elements; B denotes one or more element(s) selected from a group consisting of Mg, Ca, Sr, and Ba; C denotes one or more element(s) selected from a group consisting of Ni, Co, Mn, Al, Cr, Fe, Cu, Zn, Si, Sn, V, Nb, Ta, Ti, Zr, and Hf; and x denotes a numeral in a range from ⁇ 0.1 to 0.8; and the phase has a crystal structure belonging to a space group of R-3m and having a length ratio of the c-axis to the a-axis of the lattice constant in a range of 11.5 to 12.5; and the method includes a first
a tenth aspect of the present invention is characterized in that in the method for producing the hydrogen storage alloy of the ninth aspect, the inert gas atmosphere for carrying out the annealing is a helium gas atmosphere.
the phase having a chemical composition defined by the general formula A 5 ⁇ x B 1+x C 24 , belonging to a space group of R-3m, and having a length ratio of the c-axis to the a-axis of the lattice constant in a range of 11.5 to 12.5 is a new phase.
the first aspect of the present invention provides the hydrogen storage alloy having excellent properties such as a high retention ratio of the hydrogen storage capacity even in the case hydrogen storage and release is repeated and a high hydrogen storage capacity since the alloy contains this new phase.
the secondary battery of the eighth aspect of the present invention has a high discharge capacity and excellent durability with little decrease of a capacity retention ratio even after repeated charging and discharging with such new hydrogen storage alloy.
the ninth aspect of the present invention involves the second step of producing a solidified body by solidifying the melt at a cooling speed of not less than 1000 K/second and the third step of annealing the solidified body at 860 to 980° C. in an inert gas atmosphere in a pressurized state.
the new A 5 BC 24 phase a metastable phase which is intrinsically not so stable, can efficiently be produced.
the excellent hydrogen storage alloy having both of a high hydrogen storage capacity and a long charge-discharge cycle life can efficiently be produced.
the hydrogen storage alloy and the hydrogen storage alloy electrode according to the present invention have high hydrogen storage capacities and are excellent in the durability. Further, the secondary battery according to the present invention has a high discharge capacity and scarcely decreases the capacity retention ratio even in the case where charging and discharging are repeated. Further, the hydrogen storage alloy production method according to the present invention is capable of efficiently producing the hydrogen storage alloy having a high hydrogen storage capacity and excellent in the durability.
FIG. 1 A drawing showing one example of x-diffraction result of a hydrogen storage alloy of the present invention.
FIG. 2 A drawing three-dimensionally showing a structure model of an A 5 BC 24 phase.
FIG. 3 A drawing two-dimensionally showing a structure model of the A 5 BC 24 phase.
FIG. 4 A graph showing a difference in alloy weight alteration in accordance with the difference of inert gas atmospheres at the time of firing.
FIG. 5 A graph showing ratios (weight %) of the A 5 BC 24 phase in hydrogen storage alloys of Examples and Comparative Examples in the abscissa axis and the capacity retention ratios (%) in the ordinate axis.
the hydrogen storage alloy of the first aspect of the present invention contains a phase of a chemical composition defined by a general formula A 5 ⁇ x B 1+x C 24 , wherein in the general formula A 5 ⁇ x B 1+x C 24 , A denotes one or more element(s) selected from rare earth elements; B denotes one or more element(s) selected from a group consisting of Mg, Ca, Sr, and Ba; C denotes one or more element(s) selected from a group consisting of Ni, Co, Mn, Al, Cr, Fe, Cu, Zn, Si, Sn, V, Nb, Ta, Ti, Zr, and Hf, and x denotes a numeral in a range from ⁇ 0.1 to 0.8 and the phase has a crystal structure belonging to a space group of R-3m and having a length ratio of the c-axis to the a-axis of the lattice constant in a range of 11.5 to 12.5.
Such an A 5 BC 24 phase is a new phase which is not contained in conventional AB 3 to 3.8 type rare earth alloys and AB 5 type rare earth alloys.
the quantity of each element in the A 5 BC 24 phase can be measured by carrying out analysis of a pulverized alloy powder by x-ray diffractometry, electron probe microanalysis (EPMA), or the like and analyzing the result by a Rietveld method.
EPMA electron probe microanalysis
FIG. 1 is a graph showing the measurement result obtained by x-ray diffractometry for a hydrogen storage alloy powder having a chemical composition defined by a formula; La 17.0 Mg 4.3 Ni 70.0 Co 6.4 Mn 1.1 Al 1.1 as one embodiment of a hydrogen storage alloy of the present invention containing the A 5 BC 24 phase.
the x-ray diffractometry is carried out in the following measurement conditions.
the new A 5 BC 24 phase contained in the hydrogen storage alloy of the present invention is shown as the crystal structure model in FIG. 3 .
the new A 5 BC 24 phase has a structure in which an ABC 4 phase is inserted at certain intervals in a layered AC 5 phase.
the ABC 4 phase has a high hydrogen storage capacity. Although being inferior in the hydrogen storage capacity as compared with the ABC 4 phase, the AC 5 phase has high crystal stability and therefore is excellent in durability in the case hydrogen storage and release is repeated. As described above, due to the structure in which the ABC 4 phase is inserted at certain intervals in the layered AC 5 phase, it is supposed that the hydrogen storage alloy having a high hydrogen storage capacity and excellent in the durability is formed.
the conventional phase containing the ABC 4 phase alone has a disadvantageous point that although it has a large lattice volume and a high hydrogen storage capacity, it is difficult to release hydrogen. The reason for that is because stored hydrogen tends to stably exist among lattices.
the ABC 4 phase and the AC 5 phase are layered reciprocally. Therefore, it is supposed that the a-axis length of the ABC 4 phase is shortened so as to be compatible with the a-axis length of the AC 5 phase. It is supposed, as a result, that the stability of hydrogen positioned among the lattices is decreased and accordingly, it becomes easy to release hydrogen.
FIG. 2 shows a drawing of a unit lattice in the case the ABC 4 phase is supposed to have a hexagonal system. Accordingly, the length of the line in the bottom face of the lattice shown in FIG. 2 is an a-axis length and the height of the lattice is a c-axis length.
the content of the A 5 BC 24 phase is not particularly limited, however it is preferably 25 weight % or more in the entire hydrogen storage alloy and more preferably 45 weight % or more. Especially, in the case the content of the A 5 BC 24 phase is 65 weight % or more in the entire hydrogen storage alloy, the hydrogen storage capacity is very high and the durability is also very high.
composition of the hydrogen storage alloy is limited as defined in the second aspect and the eleventh aspect, so that an effect that the A 5 BC 24 phase can easily be produced can be obtained.
“Defined by a general formula R1 a Mg b R2 c R3 d ” described in the second and eleventh aspects does not mean that the hydrogen storage alloy contains no element other than R1, Mg, R2 and R3. It naturally means that a trace amount of an element other than R1, Mg, R2 and R3 may be contained to an extent that the effect of the invention is not affected. For instance, as the element other than R1, Mg, R2 and R3, a trace amount of Ca, Sr, Ba, Cr, Fe, Cu, Zn, Si, Sn, V, Nb, Ta, Ti, Zr, Hf, Mo, W, Pd, and Pt may be contained.
a, b, c, and d respectively satisfy 16.5 ⁇ a ⁇ 17.5, 4.2 ⁇ b ⁇ 4.5, 73 ⁇ c ⁇ 77, and 2 ⁇ d ⁇ 5. If the chemical composition satisfies the above-mentioned numeral ranges, the A 5 BC 24 phase can sufficiently be produced to obtain a hydrogen storage alloy with a very high capacity retention ratio.
La is contained as R1 and both Ni and Co are contained as R2. If so, it causes an effect to improve the hydrogen storage speed, the service life in the case hydrogen storage and release is repeated, or the ratio of the A 5 BC 24 phase in the alloy.
the durability of the hydrogen storage alloy can further be improved.
the ABC 5 phase and the AC 5 phase composing the new A 5 BC 24 phase of the hydrogen storage alloy of the present invention show big difference in the volume change in the case of absorbing hydrogen. Therefore, strains are caused in the boundaries between both phases, so that the crystal structure may possibly be changed. It is supposed that the strains may be moderated by intake of Mn and Al in the crystal of the A 5 BC 24 phase. Consequently, the durability of the hydrogen storage alloy may supposedly be improved.
the hydrogen storage alloy of the present invention is preferable to have a primary grain size of 10 to 100 nm. If the primary grain size is controlled within the range of 10 to 100 nm, the volume expansion of the hydrogen storage alloy caused along with the hydrogen storage can be moderated. As a result, powdering of the hydrogen storage alloy is hardly caused. Further, if the primary grain size is controlled within the range of 10 to 100 nm, it becomes easy to cause phase deformation by rearrangement of atoms at the time of heating treatment. Consequently, the A 5 BC 24 phase tends to be produced easily. If the primary grain size exceeds 100 nm, charging and discharging cycle deterioration tends to be caused easily due to the powdering and if it is smaller than 10 nm, deterioration due to oxidation tends to be caused easily.
the primary grain size of 10 to 100 nm means that almost all of the primary grains are in a range from the minimum of 10 nm to the maximum of 100 nm. More specifically, in the case the grain size is measured for arbitrary 100 grains in an electron microscopic photograph, the ratio of the grains having the grain size in a range of 10 to 100 nm is not less than 80% on the basis of surface area. Further, primary grains mean grains having a single-crystal structure of a single crystallite (also called as crystal grains). The method for measuring the grain size of each crystal grain is a method explained in Examples to be described later.
the method for producing the hydrogen storage alloy of the present invention is as follows.
the raw material powders of the alloy are weighed and put in a reaction container.
the raw material powders are melted using a high frequency melting furnace in an inert gas atmosphere under reduced pressure or normal pressure.
the raw material melt is quenched and solidified at a cooling speed of not lower than 1000 K/second.
the solidified raw material is annealed at 860 to 980° C. in an inert gas atmosphere in a pressurized state to produce the new A 5 BC 24 phase according to the present invention at high efficiency.
the ambient atmosphere and temperature conditions at the time of melting and annealing may properly be adjusted in accordance with the alloy composition.
the cooling speed is less than 1000 K/second, a stable phase such as a CaCu 5 type crystal structure tends to be formed easily.
the cooling speed for efficiently producing the A 5 BC 24 phase, the metastable phase is preferably 1000 K/second or higher.
the cooling method to be employed may be preferably a melt spinning method with a cooling speed of 100,000 K/second or higher, a gas atomization method with a cooling speed of about 10,000 K/second, a water cooling die casting method with a cooling speed of about 1000 K/second, or a method of quenching and solidifying on a water cooling plate.
the annealing is carried out in an inert gas atmosphere (e.g. an argon gas or a helium gas) pressurized to 0.1 MPa (gauge pressure) or higher.
an inert gas atmosphere e.g. an argon gas or a helium gas
the pressurizing condition is preferable to be controlled to 0.2 to 0.5 MPa (gauge pressure). Since helium is excellent in heat conductivity as compared with argon, the temperature difference in a firing furnace is lessened to make it possible to carry out the heating treatment of the alloy at a more uniform temperature. Heat treatment at such a uniform temperature can efficiently prevent the evaporation of alloys such as Mg and makes it possible to produce an alloy having a desired composition and a phase without altering the alloy weight.
FIG. 4 shows a graph for comparing alteration of alloy weights due to annealing in the case of annealing of a hydrogen storage alloy having a chemical composition of La 17.0 Mg 4.3 Ni 70.0 Co 6.4 Mn 1.1 Al 1.1 in an argon gas atmosphere pressurized to 0.2 MPa (gauge pressure) and in the case of annealing in a helium gas atmosphere pressurized to 0.2 MPa (gauge pressure).
the alloy weight decrease is considerably suppressed in the case of using a helium gas as compared with that in the case of using an argon gas.
the above-mentioned heating treatment temperature is 860 to 980° C., however it is preferably 880 to 930° C. If the heating treatment temperature is a temperature higher than 980° C., the ratio of production of the CuCa 5 type crystal structure phase, which is a stable phase, is increased and on the other hand, if it is a temperature lower than 860° C., the effect of the heating treatment becomes insufficient and therefore, it is not preferable. If the heating treatment temperature is within the range of 860 to 930° C., it becomes easy to produce the A 5 BC 24 phase as a main phase, that is, the phase highest in the production amount.
the hydrogen storage alloy of the present invention is used as an electrode, it is preferable to pulverize the hydrogen storage alloy. Pulverization may be carried out either before or after annealing, however, since the surface area is increased by the pulverization, it is preferable to carry out pulverization after annealing in terms of prevention of oxidation of the alloy surface.
the pulverization is preferable to be carried out in an inert atmosphere for preventing oxidation of the alloy surface.
a ball mill or the like may be employed.
the obtained powder is mixed with a proper binder (e.g. a resin such as polyvinyl alcohol) and water (or another liquid) to obtain a paste-like mixture and the mixture is packed in a nickel porous body and dried and successively the nickel porous body is pressure molded into a desired electrode shape to produce an anode usable for a secondary battery such as a nickel-hydrogen battery.
a proper binder e.g. a resin such as polyvinyl alcohol
water or another liquid
the anode produced in the above-mentioned manner is assembled with a cathode (e.g. a nickel electrode), an alkaline electrolytic solution and the like to produce a secondary battery (e.g. a nickel-hydrogen battery) of the present invention.
a cathode e.g. a nickel electrode
an alkaline electrolytic solution and the like e.g. a nickel-hydrogen battery
Respectively prescribed amounts of raw material ingots were weighed and put in a crucible to adjust the ratios by mole of elements of a hydrogen storage alloy to 17.0 for La, 4.3 for Mg, 70.2 for Ni, 6.4 for Co, 1.1 for Mn, and 1.1 for Al.
the materials were heated to 1500° C. using a high frequency melting furnace in an argon gas atmosphere at a pressure reduced to 0.06 MPa (gauge pressure) and melted. Thereafter, the material melt was transferred to a water cooling mold in the high frequency melting furnace and solidified. Further, the obtained alloy was annealed at 910° C. in a helium gas atmosphere pressurized to 0.2 MPa (gauge pressure, hereinafter the same) to obtain a hydrogen storage alloy of Example 1.
the obtained hydrogen storage alloy was mechanically pulverized by a pulverizer in an argon gas atmosphere to adjust the average grain size (D50) to be 60 ⁇ m.
Hydrogen storage alloys of Examples 2 to 51 were produced in the same conditions as described in Example 1, except that the chemical composition was changed so that the mole ratios of respective elements of the hydrogen storage alloys became as described in Table 1 and the annealing temperature was changed to the conditions described in Table 1.
Hydrogen storage alloys of Comparative Examples 1 to 14 were produced in the same conditions as described in Example 1, except that the chemical composition was changed wo that the mole ratios of respective elements of the hydrogen storage alloys became as described in Table 2 and the annealing conditions were changed to those described in Table 2.
the x-ray diffractometry was carried out for powders of the hydrogen storage alloys of Examples and Comparative Examples. Based on the obtained x-ray diffraction patterns, structure analysis was carried out by a Rietveld method (using an analysis software program RIETAN 2000). The plane indices and the diffraction angles (peak positions) of the main diffraction peaks of the A 5 BC 24 phase obtained by the Rietveld analysis for Example 1 are shown in Table 3 and the atomic arrangement of the A 5 BC 24 phase is shown in Table 4.
Co, Mn, and Al in the A 5 BC 24 phase of the hydrogen storage alloy of Example 1 are positioned in any of the sites of the atoms of Ni1 to Ni8 in Table 4.
the contents of produced phases in the respective alloys are shown in Table 5 and Table 6.
the La 5 MgNi 24 shown in Table 5 and Table 6 corresponds to the A 5 BC 24 phase of the present invention.
the term “as cast” in Table 6 means that no annealing was carried out after casting.
Example 1 910 0.0 0.79 11.03 0.0 17.38 3.24 67.55
Example 2 860 12.68 0.0 27.67 26.21 7.64 0.0 25.80
Example 3 880 9.43 0.0 25.30 25.31 9.84 0.0 30.12
Example 4 930 8.47 0.0 15.46 24.40 8.81 0.0 42.86
Example 5 980 15.61 0.0 28.97 10.89 6.94 0.0 37.59
Example 6 860 15.43 0.0 28.56 17.27 10.54 0.0 28.20
Example 7 8.80 13.85 0.0 27.44 14.56 10.75 0.0 33.40
Example 8 930 13.44 0.0 10.01 11.01 13.44 0.0 52.10
Example 9 980 21.14 0.0 10.12 9.43 20.21 0.0 39.10
Example 10 860 17.80 0.0 18.92 24.22 9.56 0.0 29.50
the chemical compositions shown in Table 1 are the compositions of the whole of the hydrogen storage alloys containing the A 5 BC 24 phase and not of the A 5 BC 24 phase. However, the respective elements shown in Table 1 are all contained in the A 5 BC 24 phase. This can be confirmed by electron probe microanalysis (EPMA).
EPMA electron probe microanalysis
Mg was used for the B element of the phase defined as the general formula A 5 ⁇ x B 1+x C 24 .
the similar results could be obtained for the cases of using Ca, Sr, or Ba belonging to the same Group IIa elements as Mg instead or for the cases of using these Group IIa elements in combination.
the average grain size and grain size distribution of the hydrogen storage alloys were measured by a laser diffraction/diffusion method using a grain size analyzer (product number: MT3000, manufactured by MicroTrack Co., Ltd.).
the average grain size means a progressive average diameter D50, that is, the grain size at the 50% point of the cumulative curve formed by setting the entire volume of the powder to be 100%.
the average grain size means the average of the size of particles formed by agglomerating primary grains and have become larger than the primary grains which will be described later.
Each anode produced in the above-mentioned manner was assembled by sandwiching them between the anodes with a separator interposed therebetween to obtain a laminated body.
the laminated body was fixed by bolts to apply a pressure of 1 kgf/cm 2 to the laminated body and an opened type cell was assembled.
an electrolytic solution was employed a mixed solution containing 6.8 mol/L of KOH and 0.8 mol/L of LiOH.
As a reference electrode an Hg/HgO electrode was used.
Each produced battery was put in a water bath at 20° C. and 10 cycles of charging and discharging were carried out in the following conditions.
the discharge capacity which was the maximum in the 10 cycles was defined as the maximum discharge capacity.
the results are shown in Tables 7 and 8.
the capacities shown in Tables 7 and 8 are the maximum discharging capacities per weight of the hydrogen storage alloys (mAh/g).
the capacity retention ratio (the ratio (%) of the discharge capacity at the 50th cycle to the discharge capacity at the 10th cycle) was calculated. The results are shown in Tables 7 and 8.
FIG. 5 shows a graph formed by plotting the ratios (weight %) of the A 5 BC 24 phase in the hydrogen storage alloys in the x-axis and the capacity retention ratios (%) in the y-axis.
Example 1 334 97.2
Example 2 328 97.9
Example 3 328 97.9
Example 4 325 98.2
Example 5 325 98.0
Example 6 323 95.1
Example 7 322 97.5
Example 8 319 97.8
Example 9 320 96.3
Example 10 319 95.2
Example 11 326 96.9
Example 12 321 97.5
Example 13 322 97.2
Example 14 327 94.5
Example 15 330 92.2
Example 16 329 93.4
Example 17 327 94.5
Example 18 301 91.8
Example 19 302 92.8
Example 20 305 94.2
Example 21 310 93.2
Example 22 318 93.1
Example 23 320 95.4
Example 24 319 97.7
Example 25 318 96.9
Example 26 322 91.5
Example 27 325 91.6
Example 28 330 92.8
Example 29 332 93.4
Example 30 321 92.5
Table 9 shows the lattice constants and the composition ratios of A: B:C of the La 5 MgNi 24 phase (same as A 5 BC 24 phase) of the hydrogen storage alloys of Examples 1 to 51 measured by the Rietveld analysis.
the description “defined by a general formula A 5 ⁇ x B 1+x C 24 ” in the first aspect does not mean that the ratio of the amount of C to the total amount of A and B is not allowed to have a margin. It naturally means that the ratio of the amount of C to the total amount of A and B may slightly be shifted from 4 to an extent that the effect of the present invention is not affected. In Examples of the present invention, there are many alloys in which the ratio of the amount of C to the total amount of A and B is slightly shifted from 4. This can be understood from Table 9. The effect of the present invention can be obtained even in these cases.

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